In this study, the efficiency of tail-to-tail dimerization of Michael acceptors catalyzed by N-heterocyclic carbene has been significantly improved. By increasing the reaction temperature to 200 degrees C, turnover number (TON) values of 146 and 185 were achieved for the dimerization of n-butyl and allyl methacrylates, respectively. Glycidyl methacrylate also underwent the dimerization without ring-opening of the epoxy group. The polymer synthesis from the resulting dimers was also demonstrated through transesterification polycondensation and thiol-ene "click" polyaddition.